Adsorption of As(V) and As(III) by nanocrystalline titanium dioxide

This study evaluated the effectiveness of nanocrystalline titanium dioxide (TiO(2)) in removing arsenate [As(V)] and arsenite [As(III)] and in photocatalytic oxidation of As(III). Batch adsorption and oxidation experiments were conducted with TiO(2) suspensions prepared in a 0.04 M NaCl solution and in a challenge water containing the competing anions phosphate, silicate, and carbonate. The removal of As(V) and As(III) reached equilibrium within 4h and the adsorption kinetics were described by a pseudo-second-order equation. The TiO(2) was effective for As(V) removal at pH<8 and showed a maximum removal for As(III) at pH of about 7.5 in the challenge water. The adsorption capacity of the TiO(2) for As(V) and As(III) was much higher than fumed TiO(2) (Degussa P25) and granular ferric oxide. More than 0.5 mmol/g of As(V) and As(III) was adsorbed by the TiO(2) at an equilibrium arsenic concentration of 0.6mM. The presence of the competing anions had a moderate effect on the adsorption capacities of the TiO(2) for As(III) and As(V) in a neutral pH range. In the presence of sunlight and dissolved oxygen, As(III) (26.7 microM or 2mg/L) was completely converted to As(V) in a 0.2g/L TiO(2) suspension through photocatalytic oxidation within 25 min. The nanocrystalline TiO(2) is an effective adsorbent for As(V) and As(III) and an efficient photocatalyst.     

Removal of As(III) and As(V) from water using a natural Fe and Mn enriched sample

The arsenic removal capacity of a natural oxide sample consisting basically of Mn-minerals (birnessite, cryptomelane, todorokite), and Fe-oxides (goethite, hematite), collected in the Iron Quadrangle mineral province in Minas Gerais, Brazil, has been investigated. As-spiked tap water and an As-rich mining effluent with As-concentrations from 100 μg L⁻¹ to 100 mg L⁻¹ were used for the experiments. Sorbent fractions of different particle sizes (<38 μm to 0.5 mm), including spherical material (diameter 2 mm), have been used. Batch and column experiments (pH values of 3.0, 5.5, and 8.5 for batch, and about pH 7.0 for column) demonstrated the high adsorption capacity of the material, with the sorption of As(III) being higher than that of As(V). At pH 3.0, the maximum uptake for As(V) and for As(III)-treated materials were 8.5 and 14.7 mg g⁻¹, respectively. The Mn-minerals promoted the oxidation of As(III) to As(V), for both sorbed and dissolved As-species. Column experiments with the cFeMn-c sample for an initial As-concentration of 100 μg L⁻¹ demonstrated a very efficient elimination of As(III), since the drinking water limit of 10 μg L⁻¹ was exceeded only after 7400 BV total throughput. The As-release from the loaded samples was below the limit established by the toxicity characteristic leaching procedure, thus making the spent material suitable for discharge in landfill deposits.     

Photochemical oxidation of As(III) by vacuum-UV lamp irradiation

In this study, vacuum-UV (VUV) lamp irradiation emitting both 185 and 254 nm lights has been investigated as a new oxidation method for As(III). Laboratory scale experiments were conducted with a batch reactor and a commercial VUV lamp. Under the experimental conditions of this study, the employed VUV lamp showed a higher performance for As(III) oxidation compared to other photochemical oxidation methods (UV-C/H(2)O(2), UV-A/Fe(III)/H(2)O(2), and UV-A/TiO2). The VUV lamp oxidized 100 microM As(III) almost completely in 10 min, and the reaction occurred mainly due to OH radicals which were produced by photo-splitting of water (H(2)O+hv (lambda=185 nm)-->OH.+H.). There was a little possibility that photo-generated H(2)O(2) acted as a minor oxidant of As(III) at alkaline pHs. The effects of Fe(III), H(2)O(2), and humic acid (HA) on the As(III) oxidation by VUV lamp irradiation were investigated. While Fe(III) and H(2)O(2) increased the As(III) oxidation efficiency, HA did not cause a significant effect. The employed VUV lamp was effective for oxidizing As(III) not only in a Milli-Q water but also in a real natural water, without significant decrease in the oxidation efficiency. Since the formed As(V) should be removed from water, activated alumina (AA) was added as an adsorbent during the As(III) oxidation by VUV lamp irradiation. The combined use of VUV lamp irradiation and AA was much more effective for the removal of total arsenic (As(tot)=As(III)+As(V)) than the single use of AA. The As(tot) removal seemed to occur as a result of the pre-oxidation of As(III) and the subsequent adsorption of As(V) on AA. Alternatively, the combination of VUV lamp irradiation and coagulation/precipitation with FeCl(3) was also an effective removal strategy for As(tot). This study shows that vacuum-UV (VUV) lamp irradiation emitting both 185 and 254 nm lights is a powerful and environmentally friendly method for As(III) oxidation which does not require additional oxidants or catalysts. The As(III) oxidation by VUV lamp irradiation was tested not only in a batch reactor but also in a flow-through quartz reactor. The As(III) oxidation rate became much faster in the latter reactor.     

Preparation and evaluation of iron–chitosan composites for removal of As(III) and As(V) from arsenic contaminated real life groundwater

A study on the removal of arsenic from real life groundwater using iron–chitosan composites is presented. Removal of arsenic(III) and arsenic(V) was studied through adsorption at pH 7.0 under equilibrium and dynamic conditions. The equilibrium data were fitted to Langmuir adsorption models and the various model parameters were evaluated. The monolayer adsorption capacity from the Langmuir model for iron chitosan flakes (ICF) (22.47 ± 0.56 mg/g for As(V) and 16.15 ± 0.32 mg/g for As(III)) was found to be considerably higher than that obtained for iron chitosan granules (ICB) (2.24 ± 0.04 mg/g for As(V); 2.32 ± 0.05 mg/g for As(III)). Anions including sulfate, phosphate and silicate at the levels present in groundwater did not cause serious interference in the adsorption behavior of arsenate/arsenite. The column regeneration studies were carried out for two sorption–desorption cycles for both As(III) and As(V) using ICF and ICB as sorbents. One hundred and forty-seven bed volumes of As(III) and 112 bed volumes of As(V) spiked groundwater were treated in column experiments using ICB, reducing arsenic concentration from 500 to <10 μg/l. The eluent used for the regeneration of the spent sorbent was 0.1 M NaOH. The adsorbent was also successfully applied for the removal of total inorganic arsenic down to <10 μg/l from real life arsenic contaminated groundwater samples.     

Preparation and evaluation of a novel Fe-Mn binary oxide adsorbent for effective arsenite removal

Arsenite (As(III)) is more toxic and more difficult to remove from water than arsenate (As(V)). As there is no simple treatment for the efficient removal of As(III), an oxidation step is always necessary to achieve higher removal. However, this leads to a complicated operation and is not cost-effective. To overcome these disadvantage, a novel Fe-Mn binary oxide material which combined the oxidation property of manganese dioxide and the high adsorption features to As(V) of iron oxides, were developed from low cost materials using a simultaneous oxidation and coprecipitation method. The adsorbent was characterized by BET surface areas measurement, powder XRD, SEM, and XPS. The results showed that prepared Fe-Mn binary oxide with a high surface area (265 m2 g(-1)) was amorphous. Iron and manganese existed mainly in the oxidation state +III and IV, respectively. Laboratory experiments were carried out to investigate adsorption kinetics, adsorption capacity of the adsorbent and the effect of solution pH values on arsenic removal. Batch experimental results showed that the adsorbent could completely oxidize As(III) to As(V) and was effective for both As(V) and As(III) removal, particularly the As(III). The maximal adsorption capacities of As(V) and As(III) were 0.93 mmol g(-1) and 1.77 mmol g(-1), respectively. The results compare favorably with those obtained using other adsorbent. The effects of anions such as SO4(2-), PO4(3-), SiO3(2-), CO3(2-) and humic acid (HA), which possibly exist in natural water, on As(III) removal were also investigated. The results indicated that phosphate was the greatest competitor with arsenic for adsorptive sites on the adsorbent. The presence of sulfate and HA had no significant effect on arsenic removal. The high uptake capability of the Fe-Mn binary oxide makes it potentially attractive adsorbent for the removal of As(III) from aqueous solution.     

Adsorption and heterogeneous oxidation of As(III) on ferrihydrite

Redox transformation of arsenic strongly influences its fate and transport in the environment. It is of interest to investigate heterogeneous oxidation of As(III) on the surface of major metal oxide in sediments. Whether As(III) can be oxidized on ferrihydrite and the role ferrihydrite plays as catalyst or oxidant are inconsistent in previous researches. In this work, oxidation of As(III) on ferrihydrite was studied by analysis of dissolved and adsorbed As(III) and As(V) quantitatively and qualitatively. X-ray absorption near edge spectroscopy (XANES) and pH_pznpc (point of zero net proton charge) of ferrihydrite with adsorbed As(III) showed clear evidence for partial oxidation on ferrihydrite. Oxidation of As(III) occurred when it was brought to contact with ferrihydrite at high Fe/As molar ratio (i.e. 50, 200). The concentration of As(V) in solid phase increased gradually while adsorbed As(III) concentration dropped. Fe(II) was not detectable during the oxidation of As(III). These results showed that ferrihydrite had the catalytic effect on oxidation of As(III). Only a fraction of As(III) was oxidized even when the system was exposed to air. The effects of ferrihydrite aging, media pH, coexistence of ions on As(III) oxidation were also investigated. The results suggest that catalytic oxidation of As(III) on ferrihydrite may play a role in geochemical cycling of arsenic in environment.     

Off-line coupled electrocatalytic oxidation and liquid phase polymer based retention (EO-LPR) techniques to remove arsenic from aqueous solutions

Electrochemistry and membrane ultrafiltration methods (electro-oxidation and liquid phase polymer based retention technique, LPR, respectively) were off-line coupled to remove As(III) inorganic species from aqueous solutions. Our main objective was to achieve an efficient extraction of arsenic species by associating a polymer-assisted liquid phase retention procedure, based on the As(V) adsorption properties of cationic water-soluble polymers, with an electrocatalytic oxidation process of As(III) into its more easily removable analogue As(V). The electrocatalytic oxidation of As(III) to As(V) was performed in the presence of different water-soluble poly(quaternary ammonium) salts acting also as supporting electrolyte, i.e. poly(vinylbenzyl)trimethyl ammonium chloride, P(ClVBTA), poly[3-(methacryloylamine)propyl]trimethyl ammonium chloride, P(ClMPTA), and poly(4-vinyl-1-methylpyridinium bromide), P(BrVMP). After complete electrocatalytic conversion of As(III) into As(V), the mixtures were introduced into an LPR cell to remove the As(V)-polymer adducts. Using P(ClMPTA), P(ClVBTA), or P(BrVMP) ammonium salts in a 20:1 polymer:As(III) mol ratio at pH 8, complete (100%) retention of the arsenic was achieved. Moreover, the As(V) retention efficiency turned out to be directly related to the net charge consumed during the electrochemical conversion of As(III) to As(V).     

A comparative study of As(III) and As(V) in aqueous solutions and adsorbed on iron oxy-hydroxides by Raman spectroscopy

The sorption of the arsenite (AsO₃³⁻) and the arsenate (AsO₄³⁻) ions and their conjugate acids onto iron oxides is one of main processes controlling the distribution of arsenic in the environment. The present work intends to provide a large vibrational spectroscopic database for comparison of As(III) and As(V) speciation in aqueous solutions and at the iron oxide - solution interface. With this purpose, ferrihydrite, feroxyhyte, goethite and hematite were firstly synthesized, characterized in detail and used for adsorption experiments. Raman spectra were recorded from As(III) and As(V) aqueous solutions at various pH conditions selected in order to highlight arsenic speciation. Raman Scattering and Diffuse Reflectance Infrared Fourier Transform (DRIFT) studies were carried out to examine the respective As-bonding mechanisms. The collected data were curve-fitted and discussed according to molecular symmetry concepts. X-ray Absorption Near Edge Spectroscopy (XANES) was applied to confirm the oxidation state of the sorbed species. The comprehensive spectroscopic investigation contributes to a better understanding of arsenic complexation by iron oxides.     

Effect of NOM on arsenic adsorption by TiO(2) in simulated As(III)-contaminated raw waters

The effect of natural organic matter (NOM) on arsenic adsorption by a commercial available TiO(2) (Degussa P25) in various simulated As(III)-contaminated raw waters was examined. Five types of NOM that represent different environmental origins were tested. Batch adsorption experiments were conducted under anaerobic conditions and in the absence of light. Either with or without the presence of NOM, the arsenic adsorption reached steady-state within 1h. The presence of 8 mg/L NOM as C in the simulated raw water, however, significantly reduced the amount of arsenic adsorbed at the steady-state. Without NOM, the arsenic adsorption increased with increasing solution pH within the pH range of 4.0-9.4. With four of the NOMs tested, the arsenic adsorption firstly increased with increasing pH and then decreased after the adsorption reached the maximum at pH 7.4-8.7. An appreciable amount of arsenate (As(V)) was detected in the filtrate after the TiO(2) adsorption in the simulated raw waters that contained NOM. The absolute amount of As(V) in the filtrate after TiO(2) adsorption was pH dependent: more As(V) was presented at pH>7 than that at pH<7. The arsenic adsorption in the simulated raw waters with and without NOM were modelled by both Langmuir and Frendlich adsorption equations, with Frendlich adsorption equation giving a better fit for the water without NOM and Langmuir adsorption equation giving a better fit for the waters with NOM. The modelling implies that NOM can occupy some available binding sites for arsenic adsorption on TiO(2) surface. This study suggests that in an As(III)-contaminated raw water, NOM can hinder the uptake of arsenic by TiO(2), but can facilitate the As(III) oxidation to As(V) at TiO(2) surface under alkaline conditions and in the absence of O(2) and light. TiO(2) thus can be used in situ to convert As(III) to the less toxic As(V) in NOM-rich groundwaters.     

Risk of arsenic transfer to a semi-confined aquifer and the effect of water level fluctuation in North Mortagne, France at a former industrial site

Groundwater contamination by arsenic was studied in the area of a former larger zinc refinery in France. Maximum contamination was observed under the former sulfuric acid factory, while the overall waste storage area was less contaminated. Arsenic concentrations there were controlled by the solubility of 3:2 calcium arsenate mineral Ca3(AsO4)2 (s) and probably a gypsum/calcium arsenate CaSO4 (s)/Ca3(AsO4)2 (s) solid solution. The speciation of As below the former sulfuric acid factory indicates an overall predominance of As(III) species. The sorption by the clay aquitard was complete for As(V), but limited to approximately 30% for As(III) under our experimental conditions. A potential risk exists, although very limited in area, of contamination of the underlying sandy aquifer and drinking water wells.     

An X-ray diffraction (XRD) and Fourier transform infrared spectroscopic (FT-IR) investigation of the long-term effect on the solidification/stabilization (S/S) of arsenic(V) in Portland cement type-V

The long-term effects on solidification/stabilization (S/S) of As5+-bearing oxyanions (AsO4(3)-) in Portland cement type-V (OPC) have been investigated by X-ray diffraction (XRD) and Fourier transform infrared spectroscopic (FT-IR) techniques. The results of this study confirm our previous results that the early hydration of cement is inhibited by the presence of AsO4(3)-, and that the inhibition is mainly caused by the formation of highly insoluble Ca3(AsO4)2 on the surface of hydrating cement particles. Arsenate analog of ettringite [Ca6(Al2O6)(SO4)3 x 32H2O] was identified in the early stages of hydration of pure Portland cement and As(V)-treated Portland cement [OPC-As(V)], but not in 10-year-old similar samples. The XRD and FT-IR results indicated interactions of oxyanions and cement particles to produce minor quantities of As5+-bearing compounds in fresh as well as in 10-year-old samples. New As5+-bearing phases, NaCaAsO4 x 7.5H2O and Ca5(AsO4)3OH were identified in the 10-year-old OPC-As(V) samples by XRD analyses. Based on these results it is concluded that Portland cement may be considered as a potential matrix to immobilize As5+-bearing wastes.     

Oxidation and removal of arsenic (III) from aerated groundwater by filtration through sand and zero-valent iron

Removing arsenic from contaminated groundwater in Bangladesh is challenging due to high concentrations of As(III), phosphate and silicate. Application of zero-valent iron as a promising removal method was investigated in detail with synthetic groundwater containing 500 microg/L As(III), 2-3mg/L P, 20mg/L Si, 8.2mM HCO3-, 2.5mM Ca2+, 1.6mM Mg2+ and pH 7.0. In a series of experiments, 1L was repeatedly passed through a mixture of 1.5 g iron filings and 3-4 g quartz sand in a vertical glass column (10mm diameter), allowing the water to re-aerate between each filtration. At a flow rate of 1L/h, up to 8 mg/L dissolved Fe(II) was released. During the subsequent oxidation of Fe(II) by dissolved oxygen, As(III) was partially oxidized and As(V) sorbed on the forming hydrous ferric oxides (HFO). HFO was retained in the next filtration step and was removed by shaking of the sand-iron mixture with water. Rapid phosphate removal provided optimal conditions for the sorption of As(V). Four filtrations lead to almost complete As(III) oxidation and removal of As(tot) to below 50 microg/L. In a prototype treatment with a succession of four filters, each containing 1.5 g iron and 60 g sand, 36 L could be treated to below 50 microg/L in one continuous filtration, without an added oxidant.     

Coprecipitation of arsenate with iron(III) in aqueous sulfate media: effect of time, lime as base and co-ions on arsenic retention

The removal and immobilization of arsenic from industrial mineral-processing effluents typically involves lime neutralization and coprecipitation of arsenate with ferric iron. Despite the wide practice and environmental importance of this technique, no laboratory study has focused on the roles of lime as base and third ions like Ca2+, Ni2+ and SO(2)4(-) on the kinetics of arsenic retention by the coprecipitates. In this work, coprecipitation was performed at 22 degrees C by fast (10 min) neutralization of industrially relevant concentrated arsenate-iron(III) (Fe/As=2, 4) acidic sulfate solutions to different pHs (4, 6, 8) in batch reactors, and the concentration of arsenic was monitored up to 1 year. The tests showed that maximum removal of arsenic was achieved upon neutralization to the target pH. Arsenic was found to be released back into solution from the precipitates upon continuing mild agitation at constant pH. Near-equilibrium was attained at different times depending on the applied pH: 10 days at pH 4, 6 months at pH 6 and 9 months at pH 8. An aging treatment at pH 4 significantly enhanced arsenic retention (arsenic release was reduced by at least 50%) after the system was finally stabilized at pH 8. The retention of arsenic at pH 8 was multifold improved (by a factor x 25) when lime was used instead of NaOH. Similarly, the retention of arsenic was enhanced by the presence of calcium and nickel ions in the starting solution. Finally, evidence of Ca(II)-Fe(III)-As(V) association was found, but not sulfate incorporation at pH 8.     

Removal of arsenic (III) and arsenic (V) from aqueous medium using chitosan-coated biosorbent

A biosorbent was prepared by coating ceramic alumina with the natural biopolymer, chitosan, using a dip-coating process. Removal of arsenic (III) (As(III)) and arsenic (V) (As(V)) was studied through adsorption on the biosorbent at pH 4.0 under equilibrium and dynamic conditions. The equilibrium adsorption data were fitted to Langmuir, Freundlich, and Redlich-Peterson adsorption models, and the model parameters were evaluated. All three models represented the experimental data well. The monolayer adsorption capacity of the sorbent, as obtained from the Langmuir isotherm, is 56.50 and 96.46 mg/g of chitosan for As(III) and As(V), respectively. The difference in adsorption capacity for As(III) and As(V) was explained on the basis of speciation of arsenic at pH 4.0. Column adsorption results indicated that no arsenic was found in the effluent solution up to about 40 and 120 bed volumes of As(III) and As(V), respectively. Sodium hydroxide solution (0.1M) was found to be capable of regenerating the column bed.     

Oxidation of arsenite in groundwater using ozone and oxygen

Oxidation of arsenite [As(III)] with ozone and oxygen was investigated in groundwater samples containing 46-62 micrograms/l total dissolved arsenic, 100-1130 micrograms/l Fe and 9-16 micrograms/l Mn. Conversion of As(III), which constituted over 70% of dissolved arsenic in the samples, to As(V) was fast with ozone, but sluggish with pure oxygen and air. Iron and manganese in the samples were also oxidized and, by sequestering the resultant As(V), played a significant role in the rate of reaction. Sorption capacity of freshly precipitated Fe(OH)3 was estimated to be 15.3 mg As/g. The kinetics of As(III) oxidation were interpreted using modified pseudo-first-order reaction. Half-lives of As(III) in experimental solutions involving saturation with each gas were approximately 4 min for the ozone reaction and, depending on the Fe concentrations, 2-5 days for pure oxygen and 4-9 days for air.     

Effects of water chemistry on arsenic removal from drinking water by electrocoagulation

Exposure to arsenic through drinking water poses a threat to human health. Electrocoagulation is a water treatment technology that involves electrolytic oxidation of anode materials and in-situ generation of coagulant. The electrochemical generation of coagulant is an alternative to using chemical coagulants, and the process can also oxidize As(III) to As(V). Batch electrocoagulation experiments were performed in the laboratory using iron electrodes. The experiments quantified the effects of pH, initial arsenic concentration and oxidation state, and concentrations of dissolved phosphate, silica and sulfate on the rate and extent of arsenic removal. The iron generated during electrocoagulation precipitated as lepidocrocite (γ-FeOOH), except when dissolved silica was present, and arsenic was removed by adsorption to the lepidocrocite. Arsenic removal was slower at higher pH. When solutions initially contained As(III), a portion of the As(III) was oxidized to As(V) during electrocoagulation. As(V) removal was faster than As(III) removal. The presence of 1 and 4 mg/L phosphate inhibited arsenic removal, while the presence of 5 and 20 mg/L silica or 10 and 50 mg/L sulfate had no significant effect on arsenic removal. For most conditions examined in this study, over 99.9% arsenic removal efficiency was achieved. Electrocoagulation was also highly effective at removing arsenic from drinking water in field trials conducted in a village in Eastern India. By using operation times long enough to produce sufficient iron oxide for removal of both phosphate and arsenate, the performance of the systems in field trials was not inhibited by high phosphate concentrations.     

Comparing polyaluminum chloride and ferric chloride for antimony removal

Antimony has been one of the contaminants required to be regulated, however, only limited information has been collected to date regarding antimony removal by polyaluminium chloride (PACl) and ferric chloride (FC). Accordingly, the possible use of coagulation by PACl or FC for antimony removal was investigated. Jar tests were used to determine the effects of solution pH, coagulant dosage, and pre-chlorination on the removal of various antimony species. Although high-efficiency antimony removal by aluminum coagulation has been expected because antimony is similar to arsenic in that both antimony and arsenic are a kind of metalloid in group V of the periodic chart, this study indicated: (1) removal density (arsenic or antimony removed per mg coagulant) for antimony by PACl was about one forty-fifth as low as observed for As(V); (2) although the removal of both Sb(III) and Sb(V) by coagulation with FC was much higher than that of PACl, a high coagulant dose of 10.5mg of FeL(-1) at optimal pH of 5.0 was still not sufficient to meet the standard antimony level of 2 microg as SbL(-1) for drinking water when around 6 microg as SbL(-1) were initially present. Consequently, investigation of a more appropriate treatment process is necessary to develop economical Sb reduction; (3) although previous studies concluded that As(V) is more effectively removed than As(III), this study showed that the removal of Sb(III) by coagulation with FC was much more pronounced than that of Sb(V); (4) oxidation of Sb(III) with chlorine decreased the ability of FC to remove antimony. Accordingly, natural water containing Sb(III) under anoxic condition should be coagulated without pre-oxidation.     

Chemical reactions between arsenic and zero-valent iron in water

Batch experiments and X-ray photoelectron spectroscopic (XPS) analyses were performed to study the reactions between arsenate [As(V)], arsenite [As(III)] and zero-valent iron [Fe(0)]. The As(III) removal rate was higher than that for As(V) when iron filings (80-120 mesh) were mixed with arsenic solutions purged with nitrogen gas in the pH range of 4-7. XPS spectra of the reacted iron coupons showed the reduction of As(III) to As(0). Soluble As(III) was formed when As(V) reacted with Fe(0) under anoxic conditions. However, no As(0) was detected on the iron coupons after 5 days of reaction in the As(V)-Fe(0) system. The removal of the arsenic species by Fe(0) was attributed to electrochemical reduction of As(III) to sparsely soluble As(0) and adsorption of As(III) and As(V) to iron hydroxides formed on the Fe(0) surface under anoxic conditions. When the solutions were open to atmospheric air, the removal rates of As(V) and As(III) were much higher than under the anoxic conditions, and As(V) removal was faster than As(III). The rapid removal of As(III) and As(V) was caused by adsorption on ferric hydroxides formed readily through oxidation of Fe(0) by dissolved oxygen.     

Removal of arsenic from water: Effects of competing anions on As(III) removal in KMnO4–Fe(II) process

Effects of sulfate, phosphate, silicate and humic acid (HA) on the removal of As(III) in the KMnO₄–Fe(II) process were investigated in the pH range of 4–9 with permanganate and ferrous sulfate applied at selected dosage. Sulfate decreased the removal of arsenic by 6.5–36.0% at pH 6–9 and the decrease in adsorption did not increase with increasing concentration of sulfate from 50 to 100 mg/L. In the presence of 1 mg/L phosphate, arsenic removal decreased gradually as pH increased from 4 to 6, and a sharp drop occurred at pH 7–9. The presence of 10 mg/L silicate had negligible effect on arsenic removal at pH 4–5 whereas decreased the arsenic removal at pH 6–9 and the decrease was more significant at higher pH. The presence of HA dramatically decreased the arsenic removal over the pH range of 6–9 and HA of higher concentration resulted in greater drop in arsenic removal. The effects of the competing anions on arsenic removal in the KMnO₄–Fe(II) process were highly dependent on pH and the degree of these four anions influencing As(III) removal decreased in the following order, phosphate > humic acid > silicate > sulfate. Sulfate differed from the other three anions because sulfate decreased the removal of arsenic mainly by competitive adsorption while phosphate, silicate and HA decreased the removal of As(III) by competitive adsorption and sequestering the formation of ferric hydroxide derived from Fe(II).     

X-ray absorption and photoelectron spectroscopic study of the association of As(III) with nanoparticulate FeS and FeS-coated sand

Iron sulfide (FeS) has been demonstrated to have a high removal capacity for arsenic (As) in reducing environments. However, FeS may be present as a coating, rather than in nanoparticulate form, in both natural and engineered systems. Frequently, the removal capacity of coatings may be different than that of nanoparticulates in batch systems. To assess the differences in removal mechanisms between nanoparticulate FeS and FeS present as a coating, the solid phase products from the reaction of As(III) with FeS-coated sand and with suspensions of nanoparticulate (NP) FeS were determined using x-ray absorption spectroscopy and x-ray photoelectron spectroscopy. In reaction with NP FeS at pH 5, As(III) was reduced to As(II) to form realgar (AsS), while at pH 9, As(III) adsorbed as an As(III) thioarsenite species. In contrast, in the FeS-coated sand system, As(III) formed the solid phase orpiment (As₂S₃) at pH 5, but adsorbed as an As(III) arsenite species at pH 9. These different solid reaction products are attributed to differences in FeS concentration and the resultant redox (pe) differences in the FeS-coated sand system versus suspensions of NP FeS. These results point to the importance of accounting for differences in concentration and redox when making inferences for coatings based on batch suspension studies.